Synthesis and theoretical analysis of palladium complexes of polydimethylsiloxane functionalised pyridine and their catalytic activity in alcohol oxidations under low polar conditions

Article abstract of DOI:10.1016/j.poly.2010.09.004

Palladium(II) complexes of polydimethylsiloxane (PDMS)-functionalised pyridine (1), [Pd(OAc)₂(1)₂] (2) and [PdCl ₂(1)₂] (3), were synthesised and characterised. The cis/trans isomerism of models of complex 3 was investigated using DFT calculations. Models of complex 2 were also theoretically analysed, to identify any possible C-H?O interactions. Complex 2 was investigated as a catalyst for selective alcohol oxidations both under solventless conditions and in supercritical carbon dioxide (scCO₂). In scCO₂ the presence of 1 was found to stabilise the palladium complex, inhibiting its decomposition to Pd(0), a stabilisation not witnessed with non-PDMS functionalised pyridine analogues.